KR101956806B1 - Polycarbonate resin composition having improved flame retardancy and transparency - Google Patents

Abstract

Disclosed is a flame retardant polycarbonate resin which, without using polytetrafluoroethylene (PTFE), improves flame retardancy and transparency while maintaining excellent mechanical properties by using a silicone-based flame retardant having a specific structure and a specific organometallic flame retardant in a specific content ratio. The present invention provides a polycarbonate resin comprising 87 to 99.89 wt% of the polycarbonate resin, 0.1 to 10 wt% of the silicone-based flame retardant, and 0.01 to 3 wt% of an organometallic flame retardant, wherein the silicone-based flame retardant is dimethyl, methoxyphenyl siloxane with phenyl silsesquioxane methoxy-terminated.

Description

TECHNICAL FIELD [0001] The present invention relates to a polycarbonate resin composition having excellent flame retardance and transparency,

The present invention relates to a polycarbonate resin composition, and more particularly, to a polycarbonate resin composition having excellent flame retardance and transparency.

Polycarbonates are widely used as engineering plastics such as exterior materials for automobiles, automobile parts, building materials, and optical parts because they have excellent heat resistance, impact resistance, electrical insulation and transparency.

On the other hand, a general polycarbonate resin has a V-2 flame retardancy according to the UL 94 V test standard. On the other hand, a high V-0 flame retardancy is required for electric and electronic products and automobile parts. Therefore, a flame retardant is added to produce a polycarbonate resin satisfying the flame retardancy of the V-0 rating to improve the flame retardancy.

Examples of the flame retardant used in the polycarbonate resin include a brominated flame retardant, a metal salt flame retardant, and a phosphorus flame retardant. Among them, brominated flame retardants are classified as environmental hormones or carcinogens, and their use is regulated. Therefore, non-halogen flame retardants are most widely applied.

However, among the non-halogen flame retardants, the metal salt flame retardant has a disadvantage of high price, and the phosphorus flame retardant is excellent in cost performance, but has a disadvantage of lowering the heat resistance and impact resistance of the polycarbonate resin.

In addition, when the metal salt flame retardant and the phosphorus flame retardant are used alone, the flame retardancy can not be enhanced sufficiently, and flame retardancy is improved by using a drip inhibitor such as polytetrafluoroethylene (PTFE), which causes a problem of lowering the transparency of the polycarbonate resin.

Korean Patent Publication No. 2010-0014492 has used a silicone flame retardant and an organometallic flame retardant in combination to impart flame retardancy to the polycarbonate resin, but the transparency of the polycarbonate resin is lowered by using PTFE.

US Patent No. 6,518,357 discloses that phenyl silsesquioxane-co-dimethylsiloxane is added to impart flame retardancy to a polycarbonate resin, but the problem that the transparency of the polycarbonate resin is lowered by using SiO ₂ , TiO ₂ , and PTFE have.

Chinese Patent Laid-Open No. 104403289 discloses a polycarbonate resin having improved flame retardancy including a benzene sulfonate silsesquioxane resin. However, there is a problem that transparency of a resin is lowered by using PTFE.

Disclosed is a flame retardant polycarbonate resin composition which is improved in flame retardancy and transparency while maintaining excellent mechanical properties.

In order to solve the above problems, the present invention provides a flame retardant composition comprising 87 to 99.89 wt% of a polycarbonate resin, 0.1 to 10 wt% of a silicon-based flame retardant, and 0.01 to 3 wt% of an organometallic flame retardant, (Dimethyl, methoxyphenyl siloxane with phenyl silsesquioxane methoxy-terminated) having a silsesquioxane structure.

The polycarbonate resin has a weight average molecular weight of 10,000 to 100,000.

Also, the present invention provides a polycarbonate resin composition characterized in that the organometallic salt-based flame retardant is potassium diphenylsulfonesulfonate.

The polycarbonate resin composition according to the following measurement method is characterized in that the flame retardancy is V-0, the transparency is 86% or more, and the Izod impact strength (23 ° C) is 86 kg · cm / to provide.

[How to measure]

The flame retardancy of the specimen made of the polycarbonate resin composition was measured according to the UL 94 V test method, and the transparency was evaluated by measuring the total light transmittance of the specimen having a thickness of 1 mm according to ASTM D1003. The transparency was evaluated according to ASTM D256 Izod impact strength (23 ° C) of 1/8 "specimen thickness was measured.

According to the present invention, flame retardancy and transparency are improved by using a silicone flame retardant having a specific structure and a specific organometallic flame retardant in a specific amount ratio without using polytetrafluoroethylene (PTFE), and a flame retardant polycarbonate A resin composition can be provided.

Hereinafter, preferred embodiments of the present invention will be described in detail. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the accompanying drawings. Throughout the specification, when an element is referred to as "including " an element, it means that it can include other elements, not excluding other elements, unless specifically stated otherwise.

The inventors of the present invention have used various additives to improve the flame retardancy of polycarbonate. However, as a result of observing the problem that the transparency and mechanical properties thereof are deteriorated, the silicon-based flame retardant and the specific organometallic flame- It has been found that excellent flame retardancy and transparency can be achieved at the same time, and an excellent impact strength can be achieved, leading to the present invention.

Accordingly, the present invention provides a flame retardant composition comprising 87 to 99.89 wt% of a polycarbonate resin, 0.1 to 10 wt% of a silicon-based flame retardant, and 0.01 to 3 wt% of an organometallic flame retardant, Dimethyl, methoxyphenyl siloxane with phenyl silsesquioxane methoxy-terminated.

Hereinafter, each component of the polycarbonate resin composition according to one embodiment of the present invention will be described in more detail.

(A) Polycarbonate resin

The polycarbonate (PC) resin used in the present invention is excellent in impact resistance, heat resistance, weather resistance, self-extinguishing ability, flexibility, processability and transparency and excellent in weatherability, Maintain performance to change.

In addition, the polycarbonate resin according to an embodiment of the present invention may have a weight average molecular weight of 10,000 to 100,000, and when the weight average molecular weight is less than 10,000, physical properties such as impact strength may be decreased, And the workability may be deteriorated. On the other hand, in the present invention, it may preferably be 25,000 to 40,000 to achieve the desired flame retardance, transparency and impact resistance including flame retardants having a specific structure.

In addition, a branched chain may be used, and preferably 0.05 to 2 mol% of a trifunctional or higher polyfunctional compound, for example, a compound having a trivalent or higher phenolic group is added to the total amount of diphenols used for polymerization A polycarbonate resin can be used.

The polycarbonate resin to be used in the present invention may be prepared according to a commonly used production method. For example, dihydroxyphenol and phosgene are reacted in the presence of a molecular weight regulator and a catalyst. Or by using an ester interchange reaction of a precursor obtained by dihydroxy phenol and diphenyl carbonate.

The polycarbonate resin may be a polymer of bisphenol-A having a melt index (300 캜, 1.2 kgf) of 3 to 28 g / 10 min, preferably 5 to 15 g / 10 min. If the melt index is less than 3 g / 10 min, the processing temperature may become high and molding may be difficult. If the melt index is more than 28 g / 10 min, the strength may be weak.

 In the present invention, the final polycarbonate resin composition is contained in an amount of 87 to 99.89% by weight, preferably 94.5 to 98.5% by weight, more preferably 96.65 to 98.5% by weight for balance of physical properties of impact resistance, heat resistance, mechanical strength, 97.85% by weight.

(B) a silicone-based flame retardant

The silicone-based flame retardant used in the present invention is added in order to impart excellent flame retardancy to the polycarbonate resin, and a flame retardant having a silsesquioxane structure is used, and in particular, the flame retardancy of the resin can be improved without using a drop- (Dimethyl, methoxyphenyl siloxane with phenyl silsesquioxane methoxy-terminated) having a phenyl silsesquioxane structure having a methoxy terminal without causing a decrease in transparency of the polycarbonate resin is used.

The silicone-based flame retardant may be contained in an amount of 0.1 to 10% by weight, preferably 1 to 5% by weight, more preferably 2 to 3% by weight based on the total composition. When the content of the silicon-based flame retardant is less than 0.1% by weight, the effect of improving the flame retardancy may be insufficient. When the content is more than 10% by weight, transparency and flame retardancy may be lowered.

(C) Organometallic salt-based flame retardant

The organometallic salt-based flame retardant used in the present invention can impart flame retardancy to the resin together with the silicon-based flame retardant, and balance flame retardance, transparency and mechanical properties without deteriorating the mechanical properties such as impact resistance.

Examples of the organic metal salt-based flame retardant include alkali metal salts and alkaline earth metal salts such as perfluoroalkanesulfonic acid, alkylbenzenesulfonic acid, halogenated alkylbenzenesulfonic acid, alkylsulfonic acid, and naphthalenesulfonic acid. Preferably, a sulfonate metal salt-based flame retardant can be used. Examples of the sulfonate metal salt include N- (p-trisulfonyl) -p-toluenesulfonamide, N- (N'-benzylaminocarbonyl) Amide, N- (phenylcarboxyl) -sulfonylamide, diphenylsulfone-3-sulfonic acid, diphenylsulfone-3,3'-disulfonic acid, isophthalic acid dimethyl-5-sulfonic acid, 2,6- Benzene sulfonic acid, o-benzene disulfonic acid, dimethyl 2,4,6-trichloro-5-sulfoisophthalate, 2,5-dichlorobenzenesulfonic acid, 2,4,5-trichlorobenzenesulfonic acid and perfluoroalkanesulfonic acid , Potassium perfluorobutanesulfonate, sodium trichlorobenzenesulfonate, and polystyrene sulfonic acid metal salts. These may be used alone or in combination of two or more. . Particularly, in order to improve the flame retardancy by mixing with a silicon-based flame retardant having a methoxy-terminated phenyl silsesquioxane structure of dimethyl, methoxyphenyl siloxane with a phenyl silsesquioxane methoxy-terminated structure, Flame retardants having a phenylsulfonesulfonate (KSS) structure may be used.

The content of the organic metal salt-based flame retardant may be 0.01 to 3 wt%, preferably 0.1 to 0.5 wt%, and more preferably 0.15 to 0.35 wt%. If the content of the organic metal salt-based flame retardant is less than 0.01% by weight, the effect of imparting flame retardancy may be insufficient. If the content is more than 3% by weight, transparency and mechanical properties may be deteriorated.

The polycarbonate composition according to the present invention thus constituted is a polycarbonate resin having excellent flame retardancy without deteriorating transparency and having improved impact strength despite the addition of a flame retardant, by using a silicone flame retardant having a specific structure in combination with a specific organometallic flame retardant And can be applied to electronic products, automobile parts, and construction materials that require flame retardance, transparency, and impact resistance.

Such a polycarbonate resin composition has a flame retardancy of V-0 grade measured according to the UL 94 V test method for a specimen of 1.5 mm in thickness and a transparency of 86% or more when the total light transmittance is measured according to ASTM D1003 And the Izod impact strength (23 ° C) of notch impact strength measured at a specimen thickness of 1/8 "according to ASTM D256 may be 86 kg · cm / cm or more, preferably 88 kg · cm / cm or more have.

The polycarbonate resin composition according to the present invention may further contain an inorganic filler and a functional additive suited to the intended use or effect, in addition to the main components described above. For example, carbon fibers, talc, a flame retardant, a light stabilizer, a lubricant, a colorant, a lubricant, a UV stabilizer, an antioxidant, a releasing agent, a coupling enhancer, a heat stabilizer, a plasticizer, have. The filler and the additive may be included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the total resin composition.

Hereinafter, a specific embodiment of the present invention will be described.

First, specifications of the polycarbonate resin (A), the silicon-based flame retardant (B), and the organometallic salt-based flame retardant (C) used in Examples and Comparative Examples of the present invention are as follows.

(A) Polycarbonate resin

Bisphenol-A type polycarbonate resin (PC-1100S, Lotte Chemical) having a weight average molecular weight of 27,000 to 33,000 was used.

(B) a silicone-based flame retardant

Dimethyl, methoxyphenyl siloxane with phenyl silsesquioxane methoxy-terminated (FR6067, Unicone) having a phenyl silsesquioxane structure having (B-1) methoxy terminal was used.

(B-2) Poly (phenyl vinyl silsesquioxane) (SST-3PV1, Gelest chemicals) was used.

(C) Organometallic salt-based flame retardant

Potassium sulfone sulfonate was used.

Example 1

(A) polycarbonate resin in an amount of 97.85% by weight, (B-1) silicone-based flame retardant in an amount of 2% by weight, and (C) organometallic flame retardant in an amount of 0.15% by weight, The composition was pelletized, dried at 100 ° C for 4 hours using a hot air drier, and injection molded into test specimens using a mold for specimen preparation.

Example 2

The specimen was formed in the same manner as in Example 1, except that the polycarbonate resin (A) was adjusted to 97.70 wt% and the organometallic salt-based flame retardant (C) was adjusted to 0.3 wt% in Example 1.

Example 3

A specimen was formed in the same manner as in Example 1, except that 95.85% by weight of the polycarbonate resin (A) and 4% by weight of the silicone flame retardant (B-1) were used in Example 1.

Example 4

A specimen was prepared in the same manner as in Example 1 except that (A) the polycarbonate resin (A) was adjusted to 95% by weight, the silicon-based flame retardant (B-1), and the organometallic salt- .

Comparative Example 1

(A) 98% by weight of a polycarbonate resin and 2% by weight of a silicone flame retardant (B-1). The thermoplastic resin composition was pelletized using a twin-screw extruder heated at 260 to 290 ° C, After drying at 100 ° C for 4 hours, the specimens were injection molded using a mold for specimen preparation.

Comparative Example 2

A specimen was formed in the same manner as in Comparative Example 1, except that (A) 88% by weight of the polycarbonate resin and (B-1) the silicon-based flame retardant were adjusted to 12% by weight in Comparative Example 1.

Comparative Example 3

(A) 99.85% by weight of a polycarbonate resin and (C) 0.15% by weight of an organometallic salt-based flame retardant. The thermoplastic resin composition was pelletized using a twin screw extruder heated at 260 to 290 ° C, After drying at 100 ° C for 4 hours, the specimens were injection molded using a mold for specimen preparation.

Comparative Example 4

A specimen was formed in the same manner as in Comparative Example 3, except that (A) 95% by weight of the polycarbonate resin and (C) the organometallic salt-based flame retardant were adjusted to 5% by weight in Comparative Example 3.

Comparative Example 5

(A) 93% by weight of a polycarbonate resin, (B-1) 2% by weight of a silicon-based flame retardant and 5% by weight of an organometallic salt-based flame retardant (C) The composition was pelletized, dried at 100 ° C for 4 hours using a hot air drier, and injection molded into test specimens using a mold for specimen preparation.

Comparative Example 6

The test piece was prepared in the same manner as in Comparative Example 5, except that (A) 87.85% by weight of the polycarbonate resin, (B-1) the silicon-based flame retardant, and the organometallic salt-based flame retardant were adjusted to 12% .

Comparative Example 7

(A) polycarbonate resin in an amount of 97.85% by weight, (B-2) a silicone-based flame retardant of 2% by weight and (C) an organometallic flame retardant of 0.15% by weight, The composition was pelletized, dried at 100 ° C for 4 hours using a hot air drier, and injection molded into test specimens using a mold for specimen preparation.

Comparative Example 8

A specimen was formed in the same manner as in Comparative Example 7, except that (A) 95.85% by weight of the polycarbonate resin and (B-2) the silicone-based flame retardant were adjusted to 4% by weight in Comparative Example 7.

Comparative Example 9

 (A) 100% by weight of a polycarbonate resin The thermoplastic resin composition was pelletized using a twin-screw extruder heated to 260 to 290 ° C, dried at 100 ° C for 4 hours using a hot air drier, The specimens were injection molded.

The component compositions according to the above Examples and Comparative Examples are summarized in the following Tables 1 (Examples) and 2 (Comparative Examples).

Test Example

The properties of each of the samples thus prepared were measured according to the following methods, and the results are shown in Tables 1 and 2 below.

(1) Flammability: The flammability of 1.5 mm thick specimens was measured according to UL 94 V flammability test method of Underwriters Laboratories.

(2) Transparency: The total light transmittance of a 1 mm thick specimen was measured according to ASTM D1003.

(3) Izod Impact Strength (23 캜): The notch impact strength of a 1/8 "specimen thickness was measured according to ASTM D256.

(A) polycarbonate resin, (B-1) silicone flame retardant and (C) organometallic flame retardant in the composition range according to the present invention (see Examples 1 to 4) It can be seen that the evaluation of flame retardancy according to UL 94 V in comparison with the case of containing only A) polycarbonate resin (Comparative Example 9) is improved to V-0 grade, transparency is maintained at 86% or more, and impact strength is also excellent.

On the other hand, when only (B-1) silicone flame retardant is added to the polycarbonate resin (A) (Comparative Example 1), transparency and impact strength are good but sufficient flame retardancy can not be obtained. (Comparative Example 2), not only the flame retardancy but also the transparency and the impact strength were lowered.

Further, when only the organometallic salt-based flame retardant (C) was added to the polycarbonate resin (A) (Comparative Example 3), transparency and impact strength were excellent but sufficient flame retardancy could not be obtained. 4) It is also seen that the flame retardancy is not improved either.

(C) is contained in an excessive amount (Comparative Example 5), the flame retardancy is improved, but the flame retardancy of the flame retardant is lower than that of the V-0 grade You can see that you can not.

(B-1) is contained in an excess amount (Comparative Example 6), the flame retardancy improving effect is not exerted, and the flame retardancy of the flame- But the transparency and the impact strength are lowered.

It can be seen that sufficient flame retardancy improving effect can not be obtained when the content range according to the present invention includes (B-1) and (B-2) different in structure (refer to Comparative Examples 7 and 8). As a result, it can be seen that the flame retardancy improving effect of the V-0 grade is realized only when the silicon-based flame retardant having the specific structure (B-1) and the specific organometallic salt-based flame retardant (C) are mixed in a specific amount.

The preferred embodiments of the present invention have been described in detail above. It will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Accordingly, the scope of the present invention is defined by the appended claims rather than the description of the invention, and all changes or modifications derived from the meaning, scope and equivalence of the claims are deemed to be included in the scope of the present invention. .

Claims (4)

87 to 99.89% by weight of a polycarbonate resin, 0.1 to 10% by weight of a silicon-based flame retardant, and 0.01 to 3% by weight of an organometallic salt-based flame retardant,
Wherein the silicon-based flame retardant is dimethyl, methoxyphenyl siloxane with phenyl silsesquioxane methoxy-terminated having a phenyl silsesquioxane structure having a methoxy terminal. The method according to claim 1,
Wherein the polycarbonate resin has a weight average molecular weight of 10,000 to 100,000. The method according to claim 1,
Wherein the organic metal salt-based flame retardant is potassium diphenylsulfonesulfonate. The method according to claim 1,
Wherein the polycarbonate resin composition has a flame retardancy of V-0 grade according to the following measurement method, a transparency of 86% or more, and Izod impact strength (23 占 폚) of 86 kg · cm / cm or more:
[How to measure]
The flame retardancy of the specimen made of the polycarbonate resin composition was measured according to the UL 94 V test method and the transparency was evaluated by measuring the total light transmittance of the specimen having a thickness of 1 mm according to ASTM D1003 and evaluated according to ASTM D256 Izod impact strength (23 ° C) of 1/8 "specimen thickness was measured.